Substituted N-aroyl N&#39;-phenyl urea compounds

ABSTRACT

Novel N-aroyl N&#39;-phenyl ureas having halogen substituents in the 3- and 5-positions and haloalkyl, haloalkoxy or haloalkylthio in the 4-position of the N&#39;-phenyl are more active and have a broader spectrum of effectiveness than the known benzoylurea insecticides.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 288,620 filedJuly 30, 1981.

BACKGROUND OF THE INVENTION

This invention relates to novel substituted N-aroyl N'-phenyl ureas, aprocess for producing them, insecticidal compositions containing themand a method for controlling certain insects.

Various insecticidal derivatives of urea are known in the art, such as,for example, U.S. Pat. Nos. 4,173,638; 4,005,223; 4,170,657; 4,139,636;4,089,975 and German Patent Application No. 3,003,113.

The N-aroyl N'-phenyl ureas of the present invention are more active andhave a broader spectrum of effectiveness than the benzoylureainsecticides currently available.

SUMMARY OF THE INVENTION

The novel compounds of this invention are N-aroyl N'-phenyl ureas havingthe formula ##STR1## wherein Ar is a substituted phenyl, or pyridylradical wherein the substituents are chloro, bromo, fluoro, C₁ -C₃ alkylor C₁ -C₃ alkoxy, with the proviso that at least one substituent ispositioned ortho to the carbonyl group; R₃ and R₄ are individually H orC₁ -C₄ alkyl or together they form the group ##STR2## Y is O or S; X₁and X₂ are halogen, and R is a C₁ -C₄ haloalkyl, haloalkoxy orhaloalkylthio group.

These novel compounds can be prepared by methods analogous to thoseknown in the art, e.g., as taught in U.S. Pat. No. 4,139,636.

The invention also provides insecticidal compositions comprising aninsecticidally effective amount of the above described N-aroyl N'-phenylureas in admixture with a suitable carrier or adjuvant therefore and amethod for killing and/or controlling insects which comprises applyingthe active compound, alone or in admixture with a carrier, to theinsects, the insect larvae or their habitats.

DETAILED DESCRIPTION OF THE INVENTION

The preferred compounds of this invention are those having the formula##STR3## where R₁ is F or Cl; R₂ is F, Cl or H; Y is O or S; X₁ and X₂are halogen and R is OCF₃, OCF₂ CHF₂, OCF₂ CHClF, OCF₂ CFHBr or OCF₂CHCl₂. Most preferably, R₁ is F or Cl R₂ is F, X₁ and X₂ are chlorineand R is OCF₂ CHClF, OCF₂ CHF₂ or OCF₂ CHFBr.

The compounds of the present invention are normally crystalline solidsof low solubility in water and of moderate solubility in many organicsolvents. The compounds have low phytotoxicity and have exceptionalactivity in the control of various undesirable agricultural, householdand veterinary insect pests.

Representative of the various insects which can be controlled by theactive compounds of the present invention are members of the ordersLepidoptera, Coleoptera, Diptera, Orthoptera, Homoptera, Thysanopteraand Acarina. They are active against normally sensitive and resistantspecies at some stages of development. Examples of insect pestscomprising the above include the tobacco budworm (Heliothis virescens),the beet armyworm (Spodoptera exigua), the Egyptian cotton leafworm(Spodoptera littoralis), the American bollworm (Heliothis armigera), thediamond-back moth (Plutella maculipennis), the gypsy moth (Lymantriadispar), the cutworm (Agrotis segetum), the Mediterranean flour moth(Ephestia kuehniella), the Colorado potato bettle (Leptinotarsadecimlineata), the mustard bettle (Phaedon cochleariae), the cotton bollweevil (Anthonomus grandis), the Mexican bean bettle (Epilachnavarivestis), the khapra bettle (Trogoderma granarium), the housefly(Musca domestica), the lesser housefly (Fannia canicularis), theMediterranean fruit fly (Ceratitis capitata), the black blow fly(Phormia regina), the cabbage rootfly (Hylemya brassicae), the yellowfever mosquito (Aedes aegypti), the malaria mosquito (Anophelesstephensi), the desert locust (Schistocerca gregaria), the migratorylocust (Locusta migratoria), the German cockroach (Blattells germanica),the American cockroach (Periplaneta americana), the pear psylla (Psyllapyricola), the onion thrips (Thrips tabaci), and the citrus rust mite(Phyllocoptruta oleivora).

The compounds are highly active and can be employed to kill insectsoutright and/or to prevent adult emergence from juvenile forms of theinsect. In such applications, the insect to be controlled and/or itshabitat is contacted or treated with an insecticidal amount of one ormore of the compounds of the present invention. The compounds may beadministered orally to warm blooded animals from which they are excretedunchanged and they effectively combat the larvae of certain fecesinhabiting insects, e.g., the face fly, horn fly and buffalo fly.

For all such uses, these compounds can be employed in unmodified form.However, the present invention embraces the use of aninsecticidally-effective amount of the active ingredients in compositionform with a material known in the art as an adjuvant or carrier.

Thus, for example, compositions employing one or a combination of theseactive ingredients can be in the form of a liquid or a dust; and theadjuvant employed can be any one of a plurality of materials includingaromatic solvents, petroleum distillates, water or other liquidcarriers, propellant substances, surface-active dispersing agents, lightabsorbers and finely-divided carrier solids.

The exact concentration of one or a combination of the compounds of thepresent invention in a composition thereof with an adjuvant thereforecan vary; it is only necessary that one or a combination of thecompounds be present in a sufficient amount so as to make possible theapplication of an insecticidally-effective or inactivating dosage.

Generally, for practical applications, one or a combination of theseactive ingredients can be broadly applied to the insect larvae or theirhabitat in compositions containing from about 0.0001 to about 98 percentby weight, preferably 5 to 50 percent by weight, of the compounds.

The invention is further illustrated by the following examples.

EXAMPLE 1 3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenylisocyanate

3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)benzenamine (12 g, 0.04mole) was added to a solution of 20 g oxalyl chloride in 100 ml CCl₄ andheated under reflux with stirring for 0.5 hour. A solid precipitated.The carbon tetrachloride and excess oxalyl chloride were removed byevaporation in a rotary evaporator. The residue (16 g) was a slightlyoily white solid, which was used in the next reaction withoutpurification.

EXAMPLE 2N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino)carbonyl)-2-chloro-3-pyridinecarboxamide##STR4##

2-Chloro-3-pyridinecarboxamide (6.3 g, 0.04 mole) and3,5-dichloro-4-(2,2-dichloro-1,1-dichloroethoxy)phenyl isocyanate(crude; 16 g, 0.04 mole) were added to 250 ml xylene and heated underreflux with stirring for two hours. After cooling in ice water, theprecipitated product was removed by suction filtration. This wasrecovered as 2-chloro-3-pyridine carboxamide. A second crop was obtainedby adding about 400 ml hexane to the filtrate. The second crop was amixture of the desired material and recovered amide. The desiredmaterial was isolated and purified by recrystallizing twice fromtoluene. M.P.=189°-192° C. NMR spectral features supported thestructural assignment.

EXAMPLE 3N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino)carbonyl)-2,6-difluoro-N-methylbenzamide##STR5##

N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino)carbonyl)-2,6-difluorobenzamide(9.9 g, 0.02 mole) and KOH (1.4 g, 87 percent purity, 0.02 mole) wereadded to 50 ml dimethylformamide with stirring, giving a clear solution.Iodomethane (3.2 g, 0.022 mole) was added and the resulting solution wasstirred at room temperature for about 24 hours. The precipitated productwas collected by suction filtration and dried. The product was purifiedby recrystallization from isopropanol. The purified product was a whitesolid melting at 153°-155° C. NMR spectral features support thestructural assignment.

Elemental Analysis: Calcd: C, 40.18; H, 1.98; N, 5.51. Found: C, 40.3;H, 2.10; N, 5.43.

EXAMPLE 4N-(((3,5-Dichloro-4-(2-chloro-1,1,2-trifluoroethoxy)phenyl)amino)carbonyl)-2,6-difluorobenzamide##STR6##

2,6-Difluorobenzoyl isocyanate (5.5 g, 0.03 mole) was added to asolution of 3,5-dichloro-4-(2-chloro-1,1,2-trifluoroethoxy)benzenamine(8.8 g, 0.03 mole) in 150 ml toluene and heated under reflux withstirring for one hour giving a clear solution. Toluene was removed byevaporation in a rotary evaporator. The residue was recrystallized fromaqueous acetic acid and then from acetonitrile giving a white solid (8.3g, 58 percent yield), melting at 178°-180° C.

Elemental analysis: Calcd: C, 40.23; H, 1.69; N, 5.87. Found: C, 40.20;H, 1.79; N, 5.83.

Employing the above procedures and appropriate starting materials, thefollowing compounds were prepared:

N-(((3,5-Dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl)amino)carbonyl)-3,5-dichloro-4-pyridinecarboxamide.##STR7##

M.P.=217°-219° C.

N-(((3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl)amino)carbonyl)-2,6-difluorobenzamide.##STR8##

M.P.=197°-199° C.

Analysis: Calcd: C, 41.67; H, 1.75; N, 6.08. Found: C, 41.8; H, 1.92; N,6.06.

N-(((3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl)amine)carbonyl)-2-chlorobenzamide.##STR9##

M.P.=173°-175° C.

Analysis: Calcd: N, 6.10. Found: N, 6.34.

3,5-Dichloro-N-(((3,5-dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino)carbonyl)-4-pyridinecarboxamide##STR10##

M.P.=228°-230° C.

N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino)carbonyl)-2-methoxybenzamide.##STR11##

M.P.=156°-158° C.

Analysis: Calcd: 41.83% C; 2.48% H; 5.74% N. Found: 41.9% C; 2.57% H;5.92% N.

N-(((3,5-Dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino)carbonyl)-2,6-difluorobenzamide.##STR12##

M.P.=199°-201° C.

Analysis: Calcd: N, 5.67. Found: N, 5.66.

2-Chloro-N-(((3,5-dichloro-4-(2,2-dichloro-1,1-difluoroethoxy)phenyl)amino(carbonyl)benzamide.##STR13##

M.P.=200°-202° C.

Analysis: Calcd: N, 5.69. Found: N, 5.60.

In addition to the above described preparative methods, many of thecompounds of this invention can be made by reacting a compound havingthe formula ##STR14## wherein all of the substituents are as abovedefined, with a haloalkene as is known in the art.

The biological activity of several of these compounds was determined. Inthe beet armyworm test, cotton leaves were dipped in aqueous suspensionsof the chemicals, dried, excised and placed into petri dishes with fivesecond-instar beet armyworm (Spodoptera exigua) larvae. Mortality countswere made five days later. The tobacco budworm test was the same exceptthat five tobacco budworm (Heliothis virescens) larvae were placed ontothe treated leaves. The results are summarized below:

    ______________________________________                                         ##STR15##                                                                    Compound     Ar           R                                                   ______________________________________                                        A            2,6-difluorophenyl                                                                         OCF.sub.2 CHCl.sub.2                                B            2-chlorophenyl                                                                             OCF.sub.2 CHCl.sub.2                                ______________________________________                                        Percent Control at Indicated Dosage, ppm                                      Beet Army Worm Test.sup.1                                                                          Tobacco Budworm Test.sup.2                               Compound                                                                              400     100      25    400   100   25                                 ______________________________________                                        A       100     100     100    100   100   80                                 B       100     100     100    100    80   40                                 ______________________________________                                         .sup.1 Untreated check mortality 0%.                                          .sup.2 Untreated check mortality 27%.                                    

Employing the above described preparative and testing methods, thecompounds listed in the following table were prepared and tested. Thetest results, LD₉₀ ppm, indicate the dosage necessary to obtain 90percent kill of the indicated insect.

    __________________________________________________________________________     ##STR16##                                                                                                           LD.sub.90, ppm                                                           Melting                                                                            Beet                                   Ex.                               Point                                                                              Army- Tobacco                          No.                                                                              R.sub.1                                                                              R.sub.2                                                                           R.sub.3                                                                          R.sub.4                                                                          Y X.sub.1                                                                         X.sub.2                                                                         R       °C.                                                                         worm  Budworm                          __________________________________________________________________________    1  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   204-206                                                                            1.6   1.6                              2  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       176-178                                                                            1.2   1.2                              3  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFBr                                                                       170-172                                                                            1.2   2.5                              4  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFI                                                                        170-172    12.5                             5  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHCl.sub.2                                                                  180-182                                                                            5.0   25.0                             6  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CH.sub.2 Cl                                                                 188-190                                                                            100.0 100.0                            7  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHBr.sub.2                                                                  215-217                                                                            25.0  400.0                            8  F      F   H  H  O Cl                                                                              Cl                                                                              OCFClCHFCl                                                                            203-205                                                                            1.25  25.0                             9  F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.3                                                                             218-220                                                                            0.6   12.5                             10 F      F   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CF.sub.3                                                                    224-227                                                                            12.5  50.0                             11 F      F   H  H  O Cl                                                                              Cl                                                                              SCF.sub.2 CHFCl                                                                       250-260                                                                            200.0 >400.0                           12 F      F   H  H  O Cl                                                                              Cl                                                                              SCF.sub.2 CHF.sub.2                                                                   166-168                                                                            3.1   12.5                             13 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       178-180                                                                            5.0   6.2                              14 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   173-175                                                                            100.0 25.0                             15 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFBr                                                                       183-185                                                                            2.5   10.0                             16 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFI                                                                        171-174    50.0                             17 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHCl.sub.2                                                                  162-164                                                                            6.2   200.0                            18 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHBr.sub.2                                                                  217-219                                                                            25.0  400.0                            19 Cl     H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.3                                                                             203-205                                                                            2.5   12.5                             20 Cl     H   H  H  S Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       137-139                                                                            10.0  200.0                            21 Cl     H   H  H  S Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   140-142                                                                            400.0 50.0                             22 F      F   H  H  S Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       149-151                                                                            12.5  12.5                             23 F      F   H  H  S Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                 24 F      H   H  H  O Cl                                                                              Cl                                                                              SCF.sub.2 CHFCl                                                                       245-250                                                                            >400.0                                                                              >400.0                           25 F      H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       165-167                                                                            100.0 25.0                             26 F      Cl  H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                 27 F      Cl  H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       205-207                                                                            2.5   5.0                              28 F      Cl  H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFBr                                                                       184-186                                                                            2.5   5.0                              29 Cl     Cl  H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   217-219                                                                            25.0  25.0                             30 Cl     Cl  H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       221-223                                                                            6.2   25.0                             31 Cl     Cl  H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFBr                                                                       200-202                                                                            100.0 12.5                             32 Cl     Cl  H  H  O Cl                                                                              Cl                                                                              SCF.sub.2 CHF.sub.2                                                                   213-215                                                                            50.0  200.0                            33 F      F   CH.sub.3                                                                         H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHCl.sub.2                                                                  153-155                                                                            100.0 >400.0                           34 F      F   CH.sub.3                                                                         H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       128-130                                                                            100.0 50.0                             35 F      F   CH.sub.3                                                                         H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   102-104                                                                            100.0 50.0                             36 F      F                                                                                  ##STR17##                                                                          O Cl                                                                              Cl                                                                              OCF.sub.2 CHCl.sub.2                                                                  194-197                                                                            400.0 >400.0                             37                                                                             F      F                                                                                  ##STR18##                                                                          O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   166-169                                                                            100.0 >400.0                             38                                                                             F      F                                                                                  ##STR19##                                                                          O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       190-192                                                                            400.0 400.0                            39 F      F   H  H  O Br                                                                              Br                                                                              OCF.sub.2 CHF.sub.2                                                                   201-203                                                                            3.7   10.0                             40 CH.sub.3                                                                             H   H  H  O Cl                                                                              Cl                                                                              OCF.sub. 2 CHFCl                                                                      163-165    >200.0                           41 CH.sub.3                                                                             CH.sub.3                                                                          H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       175-177    200.0                            42 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       182-184                                                                            100.0 400.0                            43 OCH.sub.3                                                                            H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHCl.sub.2                                                                  156-158                                                                            >400.0                                                                              >400.0                           44 OCH.sub.3                                                                            OCH.sub.3                                                                         H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       203-206                                                                            100.0 25.0                             45 OCH(CH.sub.3).sub.2                                                                  H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHFCl                                                                       239-241                                                                            >400.0                                                                              >400.0                           46 OCH(CH.sub.3).sub.2                                                                  H   H  H  O Cl                                                                              Cl                                                                              OCF.sub.2 CHF.sub.2                                                                   242-244                                                                            >400.0                                                                              >400.0                           __________________________________________________________________________

    ______________________________________                                         ##STR20##                                                                                         LD.sub.90, ppm                                                                        Beet    Tobacco                                  Ar       R          M.P., °C.                                                                       Armyworm                                                                              Budworm                                  ______________________________________                                         ##STR21##                                                                             OCF.sub.2 CHCl.sub.2                                                                     189-192   100    >400                                      ##STR22##                                                                             OCF.sub.2 CHF.sub.2                                                                      217-219  >400    >400                                      ##STR23##                                                                             OCF.sub.2 CHCl.sub.2                                                                     228-230  >400    >400                                     ______________________________________                                    

In further embodiments, the compounds of the present invention orcompositions containing the same, can be advantageously employed incombination with one or more additional pesticidal compounds. Suchadditional pesticidal compounds may be insecticides, nematocides,acaricides, herbicides, fungicides or bactericides that are compatiblewith the compounds of the present invention in the medium selected forapplication and not antagonistic to the activity of the presentcompounds. Accordingly, in such embodiments, the pesticidal compound isemployed as a supplemental toxicant for the same or for a differentpesticidal use, or as an additament. The compounds in combination cangenerally be present in the ratio of from 1 to 100 parts of the compoundof the present invention with from 100 to 1 parts of the additionalcompound(s).

The compounds of this invention are, or tend to be, slow acting, i.e.,they disrupt the molting of the insect, thereby killing it. As a result,some time can pass before the insects are killed. Accordingly, anincreased benefit can be obtained by combining the compounds of thisinvention with quicker acting insecticides such as, for example,organophosphorus compounds, carbamates and pyrethroids. Because of thisdifferent mode of action, the compounds of this invention kill orcontrol insects which have, or may be developing, resistance to the morecommon insecticides and thus they inhibit or delay the development ofresistance to such insecticides.

Various modifications may be made in the present invention withoutdeparting from the spirit or scope thereof and it is understood that welimit ourselves only as defined in the appended claims.

We claim:
 1. A compound having the formula ##STR24## wherein Ar is asubstituted phenyl radical wherein the substituents are chloro, bromo,fluoro, C₁ -C₃ alkyl or C₁ -C₃ alkoxy, with the proviso that at leastone substituent is positioned ortho to the carbonyl group; R₃ and R₄ areindividually H or C₁ -C₄ alkyl or together they form the group ##STR25##X₁ and X₂ are halogen and R is a fluorine containing C₁ -C₄ haloalkoxygroup.
 2. Compound of claim 1 having the formula ##STR26## wherein R₁ isF or Cl; R₂ is H, F or Cl and R is OCF₃, OCF₂ CHF₂, OCF₂ CHClF, OCF₂CFHBr, OCF₂ CHFI, OCFClCHFCl or OCF₂ CHCl₂.
 3. Compound of claim 2wherein Y is O; X₁ and X₂ are Cl; R₁ is F or Cl; R₂ is F or H and R isOCF₂ CHF₂, OCF₂ CHFCl or OCF₂ CHFBr.
 4. Compound of claim 3 wherein R₁and R₂ are both F and R is OCF₂ CHF₂.
 5. Compound of claim 3 wherein R₁and R₂ are both F and R is OCF₂ CHFCl.
 6. Compound of claim 3 wherein R₁and R₂ are both F and R is OCF₂ CHFBr.
 7. Compound of claim 3 wherein R₁is Cl, R₂ is H and R is OCF₂ CHF₂, OCF₂ CHFCl or OCF₂ CHFBr.
 8. Compoundof claim 3 wherein R₁ is Cl, R₂ is F and R is OCF₂ CHF₂, OCF₂ CHFCl orOCF₂ CHFBr.
 9. A composition comprising an insecticidally effectiveamount of at least one compound having the formula ##STR27## wherein Aris a substituted phenyl radical wherein the substituents are chloro,bromo, fluoro, C₁ -C₃ alkyl or C₁ -C₃ alkoxy, with the proviso that atleast one substituent is positioned ortho to the carbonyl group; R₃ andR₄ are individually H or C₁ -C₄ alkyl or together they form the group##STR28## X₁ and X₂ are halogen and R is a fluorine containing C₁ -C₄haloalkoxy group.
 10. Composition of claim 9 wherein the compound hasthe formula ##STR29## wherein R₁ is F or Cl; R₂ is H, F or Cl and R isOCF₃, OCF₂ CHF₂, OCF₂ CHClF, OCF₂ CFHBr, OCF₂ CHFI, OCFClCHFCl or OCF₂CHCl₂.
 11. Composition of claim 10 wherein Y is O; X₁ and X₂ are Cl; R₁is F or Cl; R₂ is F or H and R is OCF₂ CHF₂, OCF₂ CHFCl or OCF₂ CHFBr.12. Composition of claim 11 wherein R₁ and R₂ are both F and R is OCF₂CHF₂.
 13. Composition of claim 11 wherein R₁ and R₂ are both F and R isOCF₂ CHFCl.
 14. Composition of claim 11 wherein R₁ and R₂ are both F andR is OCF₂ CHFBr.
 15. Composition of claim 11 wherein R₁ is Cl, R₂ is Hand R is OCF₂ CHF₂, OCF₂ CHFCl or OCF₂ CHFBr.
 16. Composition of claim11 wherein R₁ is Cl, R₂ is F and R is OCF₂ CHF₂, OCF₂ CHFCl or OCF₂CHFBr.
 17. A method for killing and/or controlling insects whichcomprises applying to the insects, the insect larvae or their habitatsan insecticidally effective amount of a compound having the formula##STR30## wherein Ar is a substituted phenyl radical wherein thesubstituents are chloro, bromo, fluoro, C₁ -C₃ alkyl or C₁ -C₃ alkoxy,with the proviso that at least one substituent is positioned ortho tothe carbonyl group; R₃ and R₄ are individually H or C₁ -C₄ alkyl ortogether they form the group ##STR31## X₁ and X₂ are halogen and R is afluorine containing C₁ -C₄ haloalkoxy group.
 18. Method of claim 17wherein the compound employed has the formula ##STR32## wherein R₁ is For Cl; R₂ is H, F or Cl and R is OCF₃, OCF₂ CHF₂, OCF₂ CHClF, OCF₂CFHBr, OCF₂ CHFI, OCFClCHFCl or OCF₂ CHCl₂.
 19. Method of claim 18wherein Y is O; X₁ and X₂ are Cl; R₁ is F or Cl, R₂ is F or H and R isOCF₂ CHF₂, OCF₂ CHFCl or OCF₂ CHFBr.
 20. Method of claim 19 wherein R₁and R₂ are both F and R is OCF₂ CHF₂.
 21. Method of claim 19 wherein R₁and R₂ are both F and R is OCF₂ CHFCl .
 22. Method of claim 19 whereinR₁ and R₂ are both F and R is OCF₂ CHFBr.
 23. Method of claim 19 whereinR₁ is Cl, R₂ is H and R is OCF₂ CHF₂, OCF₂ CHFCl or OCF₂ CHFBr. 24.Method of claim 23 wherein R₁ is Cl, R₂ is F and R is OCF₂ CHF₂, OCF₂CHFCl or OCF₂ CHFBr.